US3758667A

US3758667A - Process for the preparation of mordenite

Info

Publication number: US3758667A
Application number: US00125845A
Authority: US
Inventors: H Kouwenhoven; J Cole
Original assignee: Individual
Current assignee: Individual
Priority date: 1970-10-30
Filing date: 1971-03-18
Publication date: 1973-09-11
Anticipated expiration: 1990-09-11

Abstract

High purity mordentie having a very small particle size is prepared at temperatures below 160* C by heating an aqueous mixture of amorphous silica-alumina having a silica/alumina molar ratio between 9.5 and 12.5 and one or more sodium compounds wherein at least 70 mol percent of the sodium, as Na2O, originates from sodium salts of polybasic acids having a pK value > 10 at 18* C for the highest dissociation step. The relation between the Na2O/Al2O3 molar ratio, m, in the starting mixture and the applied reaction temperature, t, which is 160* C or lower, is m 8.3-0.06 (t- 100) + OR - 2.3.

Description

United States Patent [1 1 Kouwenhoven et al.

[ 51 Sept. 11, 1973 Cole, both of 3, Badhuisweg, Amsterdam, Netherlands 22 Filed: Mar. 18,1971

21 1 Appl. No.: 125,845

[30] Foreign Application Priority Data Apr. 3, 1970 Netherlands 7015942 [56] References Cited UNITED STATES PATENTS Kouwenhoven et al. 23/113 3,328,119 6/1967 Robson 23/113 FOREIGN PATENTS OR APPLICATIONS 984,502 2/1965 Great Britain 23/1 13 OTHER PUBLlCATIONS Barrer et al. J. Chem. Soc. 1965, pages 6621-6628 Primary ExaminerEdward J. Meros Attorney.lohn M. Duncan and Glen R. Grunewald [5 7 ABSTRACT High purity mordentie having a very small particle size is prepared at temperatures below 160C by heating an aqueous mixture of amorphous silica-alumina having a silica/alumina molar ratio between 9.5 and 12.5 and one or more sodium compounds wherein at least 70 mol percent of the sodium, as Na,0, originates from sodium salts of polybasic acids having a pK value 10 at 18C for the highest dissociation step. The relation between the Na,O/Al O molar ratio, m, in the starting mixture and the applied reaction temperature, 2, which is 160C or lower, is m 8.3-0.06 (t100) 2.3.

8 Claims, No Drawings PROCESS FOR THE PREPARATION OF MORDENITE BACKGROUND OF THE INVENTION The invention relates to a process for the preparation of mordenite at a relatively low temperature, starting from amorphous silica-alumina.

Mordenite is a zeolite of the aluminosilicate type with the following composition expressed in moles of the oxides: l.0 i 0.2 Na O'Al O i 0.5 SiO It may occur either in hydrated or in dehydrated form. Mordenitev has recently become highly popular because of its suitability as a carrier material for isomerization and hydrocracking catalysts.

Zeolites of the aluminosilicate type are usually prepared by keeping an aqueous alkaline mixture comprising certain amounts of one or more aluminum compounds and one or more silicon compounds at an ele vated temperature for some time and subsequently separating the zeolite formed from the mother liquor.

A preferred method for preparing mordenite involves heating an aqueous alkaline mixture with the following composition expressed inmoles of the oxides: 1.2 2.8 Na O'A1 O 9.5-l2.5 SiO,. 60-300 H O comprising amorphous silica-alumina, sodium hydroxide and water, under pressure for 4-40 hours at a temperature of l80260C and subsequently the mordenite formed is separated from the mother liquor. This preparation method, starting from amorphous silica-alumina, offers the advantage over preparation procedures in which other aluminum and silicon sources are applied, that a synthetic mordenite is obtained which has very low contamination with zeolites different from mordenite and/or amorphous material. A drawback of this method of preparing mordenite is, however, that a relatively high reaction temperature of at least 180C is re quired. These high temperatures generate high pressures and require expensive process equipment.- Below this temperature products are formed comprising less than 80%w of mordenite and/or more than 5%w of zeolites different from mordenite. Efforts to improve the process in this respect gave rather disappointing results. Although it is possible to carry out the preparation at a lower temperature by increasing the reaction time with or without an increase of the amount of sodium hydroxide, these measures only lead to minor improvements. To prepare mordenite with the same high quality as before, a small decrease in reaction temperature requires a very large increase in reaction time. A further decrease in reaction temperature results in reaction times longer than 350 hours being required, which are no longer attractive from an economic point of view. Although increasing the concentration of sodium hydroxide in the starting mixture has a beneficial influence on the temperature-time relationship of the reaction, this measure can only be applied to a certain extent since it has appeared that if the concentration of sodium hydroxide in the starting mixture expressed as molar ratio Na O/AMO, is raised above 3.5, the mordenite prepared is contaminated with analcite. As the concentration of sodium hydroxide is further increased, more analcite is formed. In general it may be said that it is not possible to prepare, within 350 hours and at a temperature of 160C or lower, a product comprising at least 80%w of mordenite and at most 5%w of zeolites different from mordenite, from an aqueous alkaline mixture comprising amorphous silica-alumina, if sodium hydroxide is used as source for sodium.

SUMMARY OF THE INVENTION Very pure mordenite having a particle size about one tenth the normal size can be prepared from an aqueous mixture comprising amorphous silica-alumina having a silica/alumina molar ratio between 9.5 and 12.5 and one or more sodium compounds at a temperature of 160C or lower and in a reasonable time, if at least mol.% of the sodium present in the starting mixture expressed as Na,O originates from sodium salts of a certain class of polybasic acids. The polybasic acids concerned are those having a pK value 10 at 18C for the highest dissociation step, e.g., H PO and H CO The required sodium concentration in the starting mixture depends on the reaction temperature applied as follows. At a reaction temperature I as measured in degrees centigrade, the required sodium concentration in the starting mixture (m) expressed as molar ratio Na,O/Al,0, is given by the formula m 8.33-0.06 (t i 2.3, where t is 160C or lower.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the preparation'of mordenite by heating an aqueous mixture comprising amorphous silica-alumina and one or more sodium compounds, wherein at least 70 mol.% of the sodium present in the starting mixture expressed as Na,O, originates from sodium salts of polybasic acids having a pK value for the highest dissociation step measured at 18C, which is larger than lOand wherein the following relation exists between the l-Ia,()/Al,0 molar ratio (m) in the starting mixture and the applied reaction temperature (t), which amounts at most to 160C: m 8.3-0.06 (P100): 2.3.

If the preparation of mordenite according to the invention is, e.g., carried out at a temperature of C, the sodium concentration in the starting mixture expressed as-molar ratio Na,O/Al,0, should be at least 3.0 and at most 7.6. If the preparation of mordenite according to the invention is, e.g., carried out at a temperature of 100C the sodium concentration in the starting mixture expressed as molar ratio Nap/A1 0, should be at least 6.0 and at most 10.6. If at the temperatures concerned sodium concentrations outside these ranges are applied, products are formed comprising less than 80%w of mordenite and/or more than 5%w of zeolites different from mordenite. It is very surprising that in contrast with sodium hydroxide, the present sodium salts are suitable for the preparation of mordenite at temperatures of C and lower, since sodium hydroxide and the present sodium salts show a comparable performance if applied for the preparation of mordenite from amorphous silica-alumina at higher temperatures.

Sodium salts suitable for the preparation of mordenite according to the invention include sodium salts of both inorganic acids and organic acids provided that these acids fulfill the condition that the pK value of their highest dissociation step measured at 18C is larger than 10. Examples of suitable inorganic acids are P0,. Of the sodium salts used, only the sodium is incorporated in the mordenite.

In the starting mixture according to the invention, comprising amorphous silica-alumina, water and one or more of the above-defined sodium salts, minor amounts of other sodium compounds may be present. provided that their concentration expressed as moles Na o is less than 30 percent of the total sodium concentration in the starting mixture, also expressed as mole Na O. As an example of such a sodium compound sodium hydroxide may be mentioned. The preparation or mordenite according to the invention, is however, preferably carried out, starting from a mixture in which the sodium originates completely or substantially completely from one or more of the above-defined sodium salts. The amount of sodium to be applied depends on the amount of alumina present in the starting mixture and on the temperature at which the reaction is carried out. The amount of water present in the starting mixture may vary between wide limits. Usually the starting mixture contains 60-300 moles of water for each mole of alumina present therein. The amorphous silica-alumina preferably has a silica/alumina molar ratio between 9.5 and 12.5. As amorphous silica-alumina preferably a cogel of aluminum hydroxide on silica hydrogel is applied. The term cogel is used here to refer to an amorphous silica-alumina obtained by precipitating on silica hydrogel an aluminum hydroxide gel. A cogel thus defined is therefore not a coprecipitate, since in the preparation of a coprecipitate silica hydrogel and aluminum hydroxide gel are simultaneously or almost simultaneously precipitated from the solution. It is as sumed that in the cogel silica globules are covered with a layer of alumina. A very suitable method of preparing a silica-alumina cogel comprises first precipitating a silica hydrogel from an aqueous solution containing silicate ions by addition of a mineral acid, subsequently adding an aluminum salt to the mixture, and finally precipitating an aluminum hydroxide gel by addition of an alkaline-reacting solution. Instead of a cogel obtained by the above-described process, the cogel may very suitably be a commercial silica-alumina cracking catalyst with a low alumina content. Such cracking catalysts usually have an alumina content of about lll5%w, and are also obtained as a cogel.

The preparation of mordenite according to the invention is carried out by keeping the starting mixture at an elevated temperature for some time. The preparation may be carried out at atmospheric pressure as well as elevated pressure. If use is made of reaction temperatures higher than the boiling point of the mixture, it is preferred to carry out the process in an autoclave at autogeneous pressure. The preparation of mordenite according to the invention is preferably carried out at a reaction temperature betewen 95 and 155C. At these temperatures much lower pressures are gener ated than at the higher temperatures of prior processes.

From an economic point of view it is desirable to keep the reaction time as short as possible. Since the reaction time depends among other factors on the reaction temperature and on the amount of sodium present in the starting mixture, these two variables are preferably chosen in such a way in relation to each other that the formation of a very pure mordenite takes place as quickly as possible.

During the preparation, the reaction mixture is preferably agitated, since this has a beneficial influence on the yield of mordenite. This may be effected for instance by stirring, or shaking. After the formation of the mordenite, the crystals are separated from the mother liquor, for instance by filtration, decanting or centrifuging. The mass of crystals isthen washed with water and finally dried at a temperature between and 200C.

Mordenite prepared according to the invention, using a silica-alumina cogel as amorphous silicaalumina, is obtained as a very fine powder with a crystal size of from 0.1 to 10;]. Thisis about one tenth the size of mordenite particles prepared from processes which employ higher temperatures and NaOH. For some applications of mordenite is is often desirable to have the mordenite available in larger particles. For this purpose the mordenite may be mixed with an inert binder and shaped into particles with a certain form or size. This technique is well known, e.g., in the preparation of catalyst carriers, and need not be described in greater detail. Examples of suitable binders are natural clays such as kaolin and bentonite and synthetic inorganic oxides such as alumina, silica, boria and zirconia or combinations thereof, such as silica-alumina and silica-zirconia.

Mordenite prepared according to the invention may be used for various applications, such as an adsorbent, as a molecular sieve for the separation of hydrocarbon mixtures as well as for the separation of gases, as a catalyst carrier and the like. In view of itshigh degree of purity mordenite prepared according to the invention is especially suitable as a catalyst carrier. Catalysts with excellent performance in hydrocarbon conversion processes, especially isomerization and hydrocracking catalysts, can be obtained by loading the mordenite, with or without using a binder, as. described, with one or;

more metals of Group VIB, VIIB and/or VIII of the Periodic System of Elements.

The invention will now be further elucidated with the aid of the following examples.

In case reaction temperatures were applied above the boiling point of the mixture, the reaction was carried out in a closed vessel at autogeneous pressure. The composition of the products was established with the aid of X-ray analysis. In all experiments use was made of a commercial amorphous silica-alumina cracking catalyst having a water content of 25%w and comprising 14%w of alumina and 86%w of silica calculated on dry material, as amorphous silica-alumina.

EXAMPLE I TABLE I Amount of NaOH present in starting mixture, expressed as molar ratio Na,0/Al,0,

reaction time hours reaction temp.

Exp. No.

composition of the product obtained,v %w

1 L8 220 12 95 mordenite 5 amorphous material 2 2.2 200 48 95 mordenite 5 amorphous material 3 1.8 160 72 100 amorphous material 4 4 150 72 100 analcite 5 4 210 16 l analcite EXAMPLE II Eleven mixtures of the molar composition: x Na PO -Al O -10.4 SiO 253 H O were prepared by slowly adding with stirring a certain amount of Na PO 'l 2 H O to a mixture of 46 g of the above-described cracking catalyst in water. The mixtures were heated with stirring at a certain temperature and for a certain time. After the reaction mixture had cooled, the solid material was filtered ofi, washed with water until the pH of the filtrate was lower than 10 and dried at 120C. The conditions and results of these experiments are summarized in Table II.

TABLE II Amount Exp. of Na,PO reaction reaction composition of present in starttemp. time the product obing mixture, ex- "C hours tained, kw pressed as molar ratio Na,O/Al,0,

2.0 150 72 100 amorphous material 7 3.5 150 72 95 mordenite amorphous material 8 4.5 150 72 95 mordenite 5 amorphous material 9 6.0 U0 72 90 mordenite 10 amorphous material l0 8.0 150 72 50 mordenite 50 analcite l l 2.0 100 300 100 amorphous material l2 6.0 100 320 90 mordenite 10 amorphous material 13 8.0 100 320 95 mordenite 5 amorphous material 14 9.0 100 172 90 mordenite 10 amorphous material 15 10.5 I00 240 90 mordenite 3 gmelenite 7 amorphous material I6 12.0 l00 H2 50 gmelenite 50 amorphous material Of experiments ll6, only 7-9 and 12-15 are according to the present invention. The other experiments are given for comparative purposes. A chemical analysis of the products resulting from experiments 7-9 and l2-l5 showed that no phosphorus was present therein.

We claim as our invention:

1. A process for the preparation of mordenite which comprises heating an aqueous mixture of amorphous silica-alumina having a silica/alumina molar ratio between 9.5 and 12.5 and one or more sodium compounds wherein at least mol.% of the sodium present in the starting material, expressed as Na O, originates from sodium salts of polybasic acids having a pK value greater than 10 at 18C for the highest dissociation step, and wherein the molar ratio, m, of Na O/Al O in the starting mixture and the applied reaction temperature, I, which expressed in degrees centigrade is at most 160C, is m 8.3 0.06 (t-lOO) 1*: 2.3.

2. The process of claim 1 wherein the sodium salts of polybasic acids are sodium salts of orthophosphoric acid or carbonic acid.

3. The process of claim 2 wherein the sodium salt is Na PO 4. The process of claim 1 wherein the amorphous silica-alumina is a cogel of aluminum hydroxide on silica hydrogel.

5. The process of claim 4 wherein the silica-alumina cogel has been prepared by a procedure which comprises first precipitating a silica hydrogel from an aqueous solution containing silicate ions by adding a mineral acid, subsequently adding an aluminum salt to the mixture, and finally precipitating an aluminum hydroxide gel by adding an alkaline-reacting solution.

6. The process of claim 4 wherein the silica-alumina cogel is a commercial cracking catalyst with a low alumina content 7. The process of claim 1 wherein the reaction temperature is between and C.

' 8. The process of claim 1 wherin the reaction mixture is agitated during the preparation.

Claims

2. The process of claim 1 wherein the sodium salts of polybasic acids are sodium salts of orthophosphoric acid or carbonic acid.
3. The process of claim 2 wherein the sodium salt is Na3PO4.
4. The process of claim 1 wherein the amorphous silica-alumina is a cogel of aluminum hydroxide on silica hydrogel.
5. The process of claim 4 wherein the silica-alumina cogel has been prepAred by a procedure which comprises first precipitating a silica hydrogel from an aqueous solution containing silicate ions by adding a mineral acid, subsequently adding an aluminum salt to the mixture, and finally precipitating an aluminum hydroxide gel by adding an alkaline-reacting solution.
6. The process of claim 4 wherein the silica-alumina cogel is a commercial cracking catalyst with a low alumina content
7. The process of claim 1 wherein the reaction temperature is between 95* and 155*C.
8. The process of claim 1 wherin the reaction mixture is agitated during the preparation.